Cosmetic composition with a fixing and/or conditioning polymer containing a specific acrylic copolymer

ABSTRACT

The invention relates to a sprayable or vaporizable cosmetic composition, in particular in the form of an aerosol, comprising, in a cosmetically acceptable aqueous or aqueous/alcoholic medium, at least one fixing and/or conditioning polymer and at least one alkyl acrylate/alkyl methacrylate/acrylic acid copolymer.

This is a continuation of application Ser. No. 08/694,591, filed Aug. 9,1996, which is incorporated herein by reference.

The invention relates to a readily sprayable and/or vaporizable cosmeticcomposition comprising, in a cosmetically acceptable aqueous oraqueous/alcoholic medium at least one polymer selected from a fixingpolymer and a conditioning polymer and at least one specific acryliccopolymer and to the use of this specific copolymer for improving thevaporization or the spraying of the composition comprising at least onefixing and/or conditioning polymer.

Hair compositions to be sprayed onto the hair are essentially composedof a solution, in most cases aqueous/alcoholic, and of a polymer,optionally as a mixture with various cosmetic adjuvants. This solutionis packaged either in a pump-action spray or in an appropriate aerosolcontainer which is pressurized using a propellant gas.

For essentially ecological reasons, a search is underway to reduce thecompounds which are volatile at atmospheric pressure, known as VOCs(Volatile Organic Compounds), present in the compositions. The VOCs aremainly the propellants and certain solvents, such as ethanol.

Thus, legislation in certain countries has laid down a minimum VOCcontent in aerosol cosmetic compositions. In order to decrease theamount of VOC, attempts have been made to replace solvents, such asethanol, by water. These modifications can result in problems, inparticular with respect to the quality of the spraying of the spray. Thesprayed liquid particles are not fine, the spray is often narrow, i.e.,non-diffuse, and the formation of a slight foam and/or bubbles can takeplace.

As the spraying is an essential component in the final quality of acomposition to be sprayed onto hair, it is essential to overcome thesedisadvantages in order to obtain good distribution over the whole of thehair and correct fixing and/or conditioning of the hair.

European Application EP-A-590,604 describes an aqueous composition basedon an anionic acrylic copolymer and hair spray compositions comprisingthis aqueous composition based on an anionic acrylic copolymer. Thispolymerbased composition is compatible with many solvents. It exhibitsgood cosmetic properties. However, the appearance of the sprays obtainedis still unsatisfactory.

The present inventors have discovered, unexpectedly and surprisingly,that, by combining the polymers commonly used in compositions for formretention and/or for conditioning of the hairstyle with the specificanionic copolymer described above in EP-A-590,604, it is possible toobtain aqueous or aqueous/alcoholic compositions which are readilysprayable and/or vaporizable.

The subject of the present invention is therefore a cosmetic compositioncomprising, in a cosmetically acceptable aqueous or aqueous/alcoholicmedium, at least one polymer selected from a fixing polymer and aconditioning polymer and at least one acrylic copolymer formed from (a)approximately 35 to 75% by weight of an alkyl acrylate, (b)approximately 25 to 65% by weight of alkyl methacrylate and (c)approximately 1 to 15% by weight of at least one ethylenic carboxylicacid having from 3 to 5 carbon atoms, the alkyl radicals having from 1to 5 carbon atoms and these percentages being expressed by weight withrespect to the total weight of copolymer.

Another subject of the invention is the use of the copolymer describedabove for improving the quality of the vaporization or of the sprayingof cosmetic compositions packaged, for example, in a pump-action sprayor in an aerosol and comprising a fixing and/or conditioning polymer.

The sprays obtained with the compositions according to the invention canbe more diffuse and the drops can be finer. The compositions can alsoshow no or very little foaming.

In the context of the present application, cosmetic compositions forform retention of the hairstyle is understood to mean any compositionhaving the function of temporarily fixing the shape of the hairstyle,such as, for example, lacquers, hair-setting compositions and stylingsprays. Fixing power of the composition denotes the ability of thelatter to give the hair a cohesion such that the initial hair shaping ofthe hairstyle is retained.

Fixing polymer is understood to mean and polymer having the function oftemporarily fixing the shape of the hairstyle. In the context of thepresent application, conditioning polymer is understood to mean anypolymer having the function of improving the cosmetic properties ofhair, in particular softness, disentangling, feel or static electricity.

According to the invention, the acrylic copolymer described abovegenerally has a glass transition temperature of 10 to 50° C.approximately and preferably 20 to 40° C. and more particularly still 25to 35° C. This copolymer can exhibit a number-average molecular weightof 10,000 to 50,000 and preferably 20,000 to 40,000.

The alkyl acrylate is preferably chosen from methyl acrylate, ethylacrylate, propyl acrylate and butyl acrylate. Ethyl acrylate isparticularly preferred.

The concentration of alkyl acrylate is preferably 40 to 70% by weightand more particularly 50 to 60% by weight with respect to the totalweight of the copolymer.

The alkyl methacrylate is preferably chosen from methyl methacrylate,ethyl methacrylate, propyl methacrylate and butyl methacrylate. Methylmethacrylate is particularly preferred.

The concentration of alkyl methacrylate is preferably from 30 to 50% byweight and more particularly from 30 to 40% by weight with respect tothe total weight of the copolymer.

The preferred ethylenic carboxylic acids are acrylic acid, methacrylicacid, crotonic acid, itaconic acid or their mixtures. Acrylic acid andmethacrylic acid are particularly preferred. According to the invention,it is possible to use salts of these carboxylic acids.

The concentration of ethylenic carboxylic acids, or of their salts, ispreferably from 5 to 15% by weight and more particularly from 8 to 12%by weight with respect to the total weight of the copolymer.

In a particularly preferred embodiment of the invention, acrylic acid isused with methacrylic acid, each in a concentration of from 2 to 10% byweight, the total of these two acids not exceeding 15% by weight of thetotal weight of the copolymer.

The copolymer can also contain small amounts, i.e., preferably less than10%, more preferably less than 5% and most preferably less than 2%, of apolymerizable monomer other than those mentioned above.

The copolymer can be used in the form of an aqueous dispersion.Generally, the dispersion then comprises at least 0.05% of surfactantmaking possible the dispersing and the maintenance in dispersion of thepolymer.

According to the invention, it is possible to use any type of surfactantin the said dispersion but preferably a non-ionic surfactant and moreparticularly polyoxyalkylenated (C₆–C₁₂)alkyl phenols.

The mean size of the particles of the copolymer in the dispersion ispreferably from 0.1 to 1 micron.

According to a particularly preferred embodiment of the invention, useis made of a copolymer comprising 50 to 60% by weight of ethyl acrylate,30 to 40% by weight of methyl methacrylate, from 2 to 10% by weight ofacrylic acid and from 2 to 10% by weight of methacrylic acid, the totalconcentration of acrylic and methacrylic acid not exceeding 15% byweight with respect to the total weight of the acrylic copolymer.

Such a copolymer is, for example, described in European PatentApplication EP-A-590,604, the disclosure of which is hereby incorporatedby reference.

An aqueous dispersion of the acrylic copolymer described abovecomprising 25% by weight of ethyl acrylate/methylmethacrylate/methacrylic acid/acrylic acid copolymer having a glasstransition temperature of approximately 30° C. is in particular soldunder the name Amerhold DR-25 by the company Amerchol.

According to the invention, the carboxylic acid functional groups of theacrylic copolymer can be partially or completely neutralized.

According to the invention, it is possible to use any fixing and/orconditioning polymer known per se. In particular, it is possible to usea fixing and/or conditioning polymer chosen from anionic, cationic,amphoteric and non-polymers and their mixtures.

The conditioning polymers are, preferably chosen from cationic andamphoteric polymers and their mixtures. The fixing and/or conditioningpolymers can be used in the dissolved form or in the latex form (aqueousdispersion of solid polymer particles).

Thus, the anionic polymers generally used are polymers containing groupsderived from carboxylic, sulphonic or phosphoric acid and have anumber-average molecular weight of from approximately 500 to 5,000,000.

1) The carboxyl groups are introduced by unsaturated mono-ordicarboxylic acid monomers such as those corresponding to the formula(I):

in which n is an integer from 0 to 10, A denotes a methylene group,optionally connected to the carbon atom of the unsaturated group or tothe neighbouring methylene group, when n is greater than 1, via aheteroatom, such as oxygen or sulphur, R₁ denotes a hydrogen atom or aphenyl or benzyl group, R₂ denotes a hydrogen atom or a lower alkyl orcarboxyl group and R₃ denotes a hydrogen atom, a lower alkyl group or a—CH₂—COOH, phenyl or benzyl group. In the above-mentioned formula, alower alkyl radical preferably denotes a group having 1 to 4 carbonatoms and in particular methyl and ethyl.

The preferred anionic polymers containing carboxyl groups according tothe invention are:

A) Homo- or copolymers of acrylic or methacrylic acid or their salts andin particular the products sold under the names Versicol E or K by thecompany Allied Colloid or Ultrahold by the company BASF, copolymers ofacrylic acid and of acrylamide sold in the form of their sodium saltunder the names Reten 421, 423 or 425 by the Company Hercules or thesodium salts of polyhydroxycarboxylic acids.

B) Copolymers of acrylic or methacrylic acid with a monoethylenicmonomer, such as ethylene, styrene, vinyl esters or esters of acrylic ormethacrylic acid, optionally grafted onto a polyalkylene glycol, such aspolyethylene glycol, and optionally crosslinked. Such polymers aredescribed in particular in French Patent FR 1,222,944 and GermanApplication DE 2,330,956 the disclosures of which are herebyincorporated by reference, the copolymers of this type containing, intheir chain, an optionally N-alkylated and/or -hydroxyalkylatedacrylamide unit, such as described in particular in Luxembourgian PatentApplications 75370 and 75371, the disclosures of which are herebyincorporated by reference, or sold under the name Quadramer by theCompany American Cyanamid. Mention may also be made of copolymers ofacrylic acid and of C₁–C₄ alkyl methacrylate and terpolymers ofvinylpyrrolidone, of acrylic acid and of C₁–C₂₀ alkyl methacrylate, forexample lauryl methacrylate, such as that sold by the company ISP underthe name Acrylidone LM, and methacrylic acid/ethyl acrylate/tert-butylacrylate terpolymers, such as the product sold under the name Luvimer100 P by the company BASF.

C) Copolymers derived from crotonic acid, such as those containing, intheir chain, vinyl acetate or propionate units and optionally othermonomers, such as allyl or methylal esters, vinyl ether or vinyl esterof a linear or branched saturated carboxylic acid containing a longhydrocarbon chain, such as those containing at least 5 carbon atoms, itbeing possible for these polymers optionally to be grafted andcrosslinked, or alternatively a vinyl, allyl or methallyl ester of an α-or β-cyclic carboxylic acid. Such polymers are described, inter alia, inFrench Patents 1,222,944, 1,580,545, 2,265,782, 2,265,781, 1,564,110 and2,439,798, the disclosures of which are hereby incorporated byreference. Commercial products coming within this class are the resins28-29-30, 26-13-14 and 28-13-10 sold by the company National Starch.

D) Polymers derived from maleic, fumaric or itaconic acids or anhydrideswith vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivativesor acrylic acid and its esters; these polymers can be esterified. Suchpolymers are described in particular in U.S. Patent Nos. U.S. Pat. Nos.2,047,398, 2,723,248 and 2,102,113 and British Patent GB 839,805, thedisclosures of which are hereby incorporated by reference, and inparticular those sold under the names Gantrez AN or ES by the companyISP.

Polymers also coming within this class are copolymers of maleic,citraconic or itaconic anhydrides and of an allyl or methallyl ester,optionally containing an acrylamide or methacrylamide group, anα-olefin, acrylic or methacrylic esters, acrylic or methacrylic acids orvinylpyrrolidone in their chain; the anhydride functional groups aremonoesterified or monoamidified. These polymers are, for example,described in French Patents 2,350,384 and 2,357,241 assigned to thepresent assignee, the disclosures of which are hereby incorporated byreference.

E) Polyacrylamides containing carboxylate groups.

2) The polymers comprising sulpho groups are polymers containingvinylsulpho, styrenesulpho, naphthalenesulpho or acrylamidoalkylsulphounits.

These polymers can in particular be selected from:

-   -   salts of polyvinylsulphonic acid having a number-average        molecular weight of from approximately 1000 to 100,000, as well        as copolymers with an unsaturated comonomer, such as acrylic or        methacrylic acids and their esters, as well as acrylamide or its        derivatives, vinyl ethers and vinylpyrrolidone.    -   Salts of polystyrenesulphonic acid, the sodium salts having a        number-average molecular weight of approximately 500,000 and of        approximately 100,000 sold respectively under the names Flexan        500 and Flexan 130 by National Starch. These compounds are        described in French Patent FR 2,198,719, the disclosure of which        is hereby incorporated by reference.    -   Salts of polyacrylamidesulphonic acids, those mentioned in U.S.        Pat. No. 4,128,631, the disclosure of which is hereby        incorporated by reference, and more particularly salts of        polyacrylamidoethylpropanesulphonic acid.

According to the invention, the anionic polymers are preferably chosenfrom copolymers of acrylic acid, such as the acrylic acid/ethylacrylate/N-tert-butylacrylamide terpolymer sold under the name UltraholdStrong by the company BASF, copolymers derived from crotonic acid, suchas the vinyl acetate/vinyl tert-butylbenzoate/crotonic acid terpolymersand the crotonic acid/vinyl acetate/vinyl neododecanoate terpolymerssold under the name Resin 28-29-30 by the company National Starch,polymers derived from maleic, fumaric or itaconic acids or anhydrideswith vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivativesor acrylic acid and its esters, such as the monoesterified maleicanhydride/methyl vinyl ether copolymer sold under the name Gantrez ES425 by the company ISP, copolymers of methacrylic acid and of methylmethacrylate sold under the name Eudragit L by the company Rohm Pharma,the copolymer of methacrylic acid and of ethyl acrylate sold under thename Luvimer Maex by the company BASF, the vinylpyrrolidone/acrylicacid/lauryl methacrylate terpolymer sold under the name Acrylidone LM bythe company ISP or the methacrylic acid/ethyl acrylate/tert-butylacrylate terpolymer sold under the name Luvimer 100 P by the companyBASF.

The cationic poly which can be used according to the present inventionare preferably chosen from polymers containing primary, secondary,tertiary and/or quaternary amine groups forming part of the polymerchain or directly connected to the latter and having a number-averagemolecular weight of from 500 to approximately 5,000,000 and preferablyfrom 1000 to 3,000,000.

In the context of fixing cationic polymers, preference is given tocationic polymers with a conductivity of less than or equal to 1 mohm⁻¹cm⁻¹ and which have a viscosity, at 1% in water, of less than 20 cps (20mPa·s). The viscosity is measured using a Rheomat RM 180 (Contraves TV,rotor 1) from Mettler.

Mention may more particularly be made, among these polymers, of thefollowing cationic polymers:

(1) Homopolymers or copolymers derived from acrylic or methacrylicesters or amides and containing at least one of the units of followingformulae:

in which:

-   R₃ denotes H or CH₃;-   A is a linear or branched alkyl group containing 1 to 6 carbon atoms    or a hydroxyalkyl group containing 1 to 4 carbon atoms;-   R₄, R₅ and R₆, which are identical or different, represent an alkyl    group having from 1 to 18 carbon atoms or a benzyl radical;-   R₁ and R₂ represent hydrogen or an alkyl group having from 1 to 6    carbon atoms;-   X denotes a methyl sulphate anion or a halide, such as chloride or    bromide.

The copolymers of the family (1) additionally contain one or a number ofunits deriving from comonomers which can be chosen from the family ofacrylamides, methacrylamides, diacetone acrylamides, acrylamides andmethacrylamides substituted on the nitrogen by lower alkyls, acrylic ormethacrylic acids or their esters, vinyllactams, such asvinylpyrrolidone or vinylcaprolactam, or vinyl esters.

Thus, mention may be made, among these copolymers of the family (1), of:

-   -   the copolymer of acrylamide and of dimethylaminoethyl        methacrylate, quaternized with dimethyl sulphate, sold under the        name Hercofloc by the company Hercules,    -   copolymers of acrylamide and of        methacryloyloxyethyltrimethylammonium chloride described, for        example, in European Patent Application EP-A-080,976, the        disclosure of which is hereby incorporated by reference, and        sold under the name Bina Quat P 100 by the company Ciba-Geigy,    -   the copolymer of acrylamide and of        methacryloyloxyethyltrimethylammonium methyl sulphate sold under        the name Reten by the company Hercules,    -   optionally quaternized vinylpyrrolidone/dialkylaminoalkyl        acrylate or methacrylate copolymers, such as the products sold        under the name “Gafquat” by the company ISP, such as, for        example, “Gafquat 734” or “Gafquat 755”, or alternatively the        products named “Copolymer 845, 958 and 937”. These polymers are        described in detail in French Patents 2,077,143 and 2,393,573,        the disclosures of which are hereby incorporated by reference,    -   the dimethylaminoethyl        methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymer, such        as the product sold under the name Gaffix VC 713 by the company        ISP,    -   and the quaternized        dimethylaminopropyl-methacrylamide/vinylpyrrolidone copolymer,        such as the product sold under the name “Gafquat HS 100” by the        company ISP.

(2) Quaternized polysaccharides, described more particularly in U.S.Pat. Nos. 3,589,578 and 4,031,370, the disclosures of which are herebyincorporated by reference, such as the product sold under the nameJaguar C 13 S by the company Meyhall.

(3) Quaternary copolymers of vinylpyrrolidone and of vinylimidazole.

(4) Chitosans or their salts;

the salts which can be used are in particular chitosan acetate, lactate,glutamate, gluconate or pyrrolidonecarboxylate.

Mention may be made, among these compounds, of chitosan having a degreeof deacetylation of 90.5% sold under the name Kytan Crude Standard bythe company Aber Technologies or chitosan pyrrolidonecarboxylate soldunder the name Kytamer PC by the company Amerchol.

The amphoteric polymers which can be used in accordance with theinvention can be chosen from polymers containing A and B unitsdistributed statistically in the polymer chain, where A denotes a unitderiving from a monomer containing at least one basic nitrogen atom andB denotes a unit deriving from an acidic monomer containing one or anumber of carboxyl or sulpho groups or alternatively A and B can denotegroups deriving from zwitterionic carboxybetaine or sulphobetainemonomers.

A and B can also denote a cationic polymer chain containing primary;secondary, tertiary or quaternary amine groups, in which at least one ofthe amine groups carries a carboxyl or sulpho group connected via ahydrocarbon radical or alternatively A and B form part of a chain of apolymer containing an α, β-dicarboxy ethylene unit in which one of thecarboxyl groups has been reacted with a polyamine containing one or anumber of primary or secondary amine groups.

The more particularly preferred amphoteric polymers corresponding to thedefinition given above are chosen from the following polymers:

(1) Polymers resulting from the copolymerization of a monomer derivedfrom a vinyl compound carrying a carboxyl group, such as moreparticularly acrylic acid, methacrylic acid, maleic acid orα-chloroacrylic acid, and of a basic monomer derived from a substitutedvinyl compound containing at least one basic atom, such as moreparticularly dialkylaminoalkyl methacrylate and acrylate ordialkylaminoalkylmethacrylamide and acrylamide. Such compounds aredescribed in U.S. Pat. No. 3,836,537, the disclosure of which is herebyincorporated by reference.

(2) Polymers derived from diallyldialkylammonium and from at least oneanionic monomer, such as polymers containing approximately 60 toapproximately 99% by weight of units derived from a quaternarydiallyldialkylammonium monomer, in which the alkyl groups areindependently chosen from alkyl groups having 1 to 18 carbon atoms andin which the anion is derived from an acid having an ionization constantgreater than 10⁻¹³, and 1 to 40%, by weight of this polymer, of ananionic monomer chosen from acrylic or methacrylic acids, thenumber-average molecular weight of this polymer being from approximately50,000 to 10,000,000, determined by gel permeation chromatography. Suchpolymers are described in European Application EP-A269,243, thedisclosure of which is hereby incorporated by reference.

The preferred polymers are, inter alia, polymers containing alkyl groupsselected from groups having 1 to 4 carbon atoms and more particularlymethyl and ethyl groups.

Among these polymers, copolymers of dimethyldiallylammonium or ofdiethyldiallylammonium chloride and of acrylic acid are particularlypreferred. These polymers are, for example, sold under the names“Merquat 280” and “Merquat 295” by the company Merck. It is alsopossible to use the dimethyldiallylammonium chloride/acrylicacid/acrylamide terpolymers sold under the name “Merquat Plus 3330” bythe company Merck.

(3) Polymers containing units deriving:

-   -   a) from at least one monomer selected from acrylamides or        methacrylamides substituted on the nitrogen by an alkyl radical,    -   b) from at least one acidic comonomer containing one or a number        of reactive carboxyl groups, and    -   c) from at least one basic comonomer, such as esters containing        primary, secondary, tertiary and/or quaternary amine        substituents of acrylic and methacrylic acids and the product        from the quaternization of dimethylaminoethyl methacrylate with        dimethyl or diethyl sulphate.        The more particularly preferred N-substituted acrylamides or        methacrylamides according to the invention are the groups in        which the alkyl radicals contain from 2 to 12 carbon atoms and        more particularly N-ethylacrylamide, N-tert-butylacrylamide,        N-tert-octylacrylamide, N-octylacrylamide, N-decylacrylamide or        N-dodecylacrylamide, and the corresponding methacrylamides.

The acidic comonomers are more particularly chosen from acrylic,methacrylic, crotonic, itaconic, maleic and fumaric acids and the alkylmonoesters, having 1 to 4 carbon atoms, of maleic or fumaric acids oranhydrides.

The preferred basic comonomers are aminoethyl, butylaminoethyl,N,N′-dimethylaminoethyl and N-tert-butylaminoethyl methacrylates.

Use is particularly made of copolymers whose CTFA name (4th Ed., 1991)is Octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer,such as the products sold under the name Amphomer or Lovocryl 47 by thecompany National Starch.

(4) Partially or totally alkylated and crosslinked polyaminoamidesderiving from polyaminoamides of general formula (II):—[—CO—R₁₀—CO—Z—]—  (II)in which R₁₀ represents a divalent radical derived from a saturateddicarboxylic acid, from an aliphatic mono- or dicarboxylic acidcontaining an ethylenic double bond, from an ester of a lower alkanolhaving 1 to 6 carbon atoms of these acids or from a radical derivingfrom the reaction of any one of the said acids with a bisprimary orbissecondary amine and Z denotes a radical from a bisprimary or mono- orbissecondary polyalkylenepolyamine and preferably represents:

-   -   a) in the proportions of 60 to 100 mol %, the radical (III)        —NH—[—(CH₂)_(x)—NH—]_(n)—  (III)        where x=2 and n=2 or 3 or alternatively x=3 and n=2, this        radical deriving from diethylenetriamine, triethylenetetraamine        or dipropylenetriamine;    -   b) in the proportions of 0 to 40 mol %, the above radical (III),        in which x=2 and n=1 and which derives from ethylenediamine, or        the radical deriving from piperazine:

-   -   c) in the proportions of 0 to 20 mol %, the —NH—(CH₂)₆—NH—        radical deriving from hexamethylenediamine, these        polyaminoamides being crosslinked by addition of a bifunctional        crosslinking agent chosen from epihalohydrins, diepoxides,        dianhydrides or bisunsaturated derivatives, by means of 0.025 to        0.35 mol of crosslinking agent per amine group of the        polyaminoamide, and alkylated by reaction with acrylic acid,        with chloroacetic acid or with an alkanesultone, or with their        salts.

The saturated carboxylic acids are preferably chosen from acids having 6to 10 carbon acids, such as adipic, 2,2,4-trimethyl- and2,4,4-trimethyladipic or terephthalic acid, acids containing anethylenic double bond, such as, for example, acrylic, methacrylic anditaconic acids.

The alkanesultones used in the alkylation are preferably propane- orbutanesultone and the salts of the alkylating agents are preferably thesodium or potassium salts.

(5) Polymers containing zwitterionic units of formula (IV):

in which R₁₁ denotes a polymerizable unsaturated group, such as anacrylate, methacrylate, acrylamide or methacrylamide group, x and yrepresent an integer from 1 to 3, R₁₂ and R₁₃ represent hydrogen,methyl, ethyl or propyl and R₁₄ and R₁₅ represent a hydrogen atom or analkyl radical, so that the sum of the carbon atoms in R₁₄ and R₁₅ doesnot exceed 10.

The polymers comprising such units can also contain units derived fromnon-zwitterionic monomers, such as vinylpyrrolidone, dimethyl- ordiethylaminoethyl acrylate or methacrylate or alkyl acrylates ormethacrylates, acrylamides or methacrylamides or vinyl acetate. Mentionmay be made, by way of example, of the methyl methacrylate/methyldimethylcarboxymethyl! ammonioethylmethacrylate copolymer, such as theproduct sold under the name Diaformer by the company Sandoz.

(6) Polymers derived from chitosan containing monomer unitscorresponding to the following formulae:

the D unit being present in proportions of from 0 to 30%, the E unit inproportions of from 5 to 50% and the F unit in proportions of from 30 to90%, it being understood that, in this F unit, R₁₆ represents a radicalof formula:

in which, if n=0, R₁₇, R₁₈ and R₁₉, which are identical or different,each represent a hydrogen atom, a methyl, hydroxyl, acetoxy or aminoresidue, a monoalkylamino residue or a dialkylamino residue, which areoptionally interrupted by one or a number of nitrogen atoms and/oroptionally substituted by one or a number of amino, hydroxyl, carboxyl,alkylthio or sulpho groups, or an alkylthio residue, in which the alkylgroup carries an amino residue, at least one of the R₁₇, R₁₈ and R₁₉radicals being, in this case, a hydrogen atom;

-   -   or, if n=1, R₁₇, R₁₈ and R₁₉ each represent a hydrogen atom, and        the salts formed by these compounds with bases or acids.

(7) Polymers derived from the N-carboxyalkylation of chitosan, such asN-(carboxymethyl)chitosan or N-(carboxybutyl)chitosan sold under thename “Evalsan” by the company Jan Dekker.

(8) Polymers corresponding to the general formula (V) described inFrench Patent 1,400,366, the disclosure of which is hereby incorporatedby reference:

in which R₂₀ represents a hydrogen atom or a CH₃O, CH₃CH₂O or phenylradical R₂₁ denotes hydrogen or a lower alkyl radical, such as methyl orethyl, R₂₂ denotes hydrogen or a lower alkyl radical, such as methyl orethyl, and R₂₃ denotes a lower alkyl radical, such as methyl or ethyl,or a radical corresponding to the formula: —R₂₄—N(R₂₂)₂, R₂₄representing a CH₂—CH₂—, —CH₂—CH₂—CH₂— or —CH₂—CH(CH₃)-group and R₂₂having the meanings mentioned above, and the higher homologues of theseradicals containing up to 6 carbon atoms.

(9) Amphoteric polymers of the -A-Z-A-Z type chosen from:

-   -   a) the polymers obtained by reacting chloroacetic acid or sodium        chloroacetate with compounds containing at least one unit of        formula:        -A-Z-A-Z-A-  (VI)        where A denotes a radical

and Z denotes the B or B′ symbol, B or B′, which are identical ordifferent, denote a divalent radical which is a straight- orbranched-chain alkylene radical containing up to 7 carbon atoms in themain chain, which is unsubstituted or substituted by hydroxyl groups,and which can additionally contain oxygen, nitrogen or sulphur atoms or1 to 3 aromatic and/or heterocyclic rings; the oxygen, nitrogen andsulphur atoms being present in the form of ether, thioether, sulphoxide,sulphone, sulphonium, alkylamine or alkenylamine groups or hydroxyl,benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol,ester and/or urethane groups.

-   -   b) The polymers of formula:        -A-Z-A-Z-  (VI′)        where A denotes a radical

and Z denotes the B or B′ symbol and at least once B′, B having themeaning indicated above and B′ is a divalent radical which is astraight- or branched-chain alkylene radical having up to 7 carbon atomsin the main chain, the radical being unsubstituted or substituted by oneor a number of hydroxyl radicals, and containing one or a number ofnitrogen atoms, the nitrogen atom being substituted by an alkyl chainoptionally interrupted by an oxygen atom and necessarily containing oneor a number of carboxyl functional groups or one or a number of hydroxylfunctional groups betainized by reaction with chloroacetic acid orsodium chloroacetate.

(10) (C₁–C₅)alkyl vinyl ether/maleic anhydride copolymers in which themaleic anhydride has been partially modified by semiamidification withan N,N-dialkylaminoalkylamine, such as N,N-dimethylaminopropylamine, orby semiesterification with an N,N-dialkanolamine. These copolymers canalso contain other vinyl comonomers, such as vinylcaprolactam.

The particularly preferred amphoteric polymers according to theinvention are those from the family (3), such as the copolymers whoseCTFA name is Octylacrylamide/acrylates/butylaminoethyl methacrylatecopolymer, such as the products sold under the name Amphomer or Lovocryl47 by the company National Starch.

The fixing and/or conditioning polymer or polymers are, for example,present in concentrations of from 0.1% to 20% by weight, and preferablyin concentrations of from 1% to 10% by weight, with respect to the totalweight of the composition.

The concentration of acrylic copolymer is generally from 0.01 to 15% byweight with respect to the total weight of the composition andpreferably from 0.05 to 8% by weight.

The ratio by weight of the fixing and/or conditioning polymer to theacrylic copolymer can be from 0.1:1 to 10:1 and preferably from 0.5:1 to5:1.

The cosmetically acceptable medium is preferably composed of water or amixture of water and of cosmetically acceptable solvents, such asmonoalcohols, polyalcohols or glycol ethers, which can be used alone oras a mixture.

Mention may more particularly be made of lower alcohols, such as ethanolor isopropanol, polyalcohols, such as diethylene glycol, or glycolethers, such as the alkyl ethers of glycol or of diethylene glycol.

The concentration of solvents is generally from 0 to 80% by weight andpreferably from 0 to 55% by weight with respect to the total weight ofthe composition.

The cosmetically acceptable medium is preferably composed essentially ofwater.

The pH of the compositions according to the invention is generally from2 to 9 and in particular from 3 to 8. It can be adjusted to the chosenvalue by means of basifying or acidifying agents commonly used incosmetics for this type of application.

When the composition according to the invention is pressurized in theform of an aerosol, for the purpose of obtaining a lacquer, it comprisesat least one propellant agent which can be chosen from volatilehydrocarbons, such as n-butane, propane, isobutane or pentane,chlorinated and/or fluorinated hydrocarbons and their mixtures. Carbondioxide gas, nitrous oxide, dimethyl ether, nitrogen, compressed air andtheir mixtures can also be used as propellant agent.

The concentration of propellant is generally from 10 to 50% by weightwith respect to the total weight of the pressurized composition andpreferably from 15 to 35% by weight.

The compositions according to the invention, whether pressurized or not,can additionally contain surface-active agents, preserving agents,sequesterants, softeners, fragrances, dyes, viscosity-modifying agents,foam-modifying agents, antifoaming agents, pearlescence agents,moisturizing agents, anti-dandruff agents, anti-seborrhoeic agents,sunscreening agents, proteins, vitamins, plasticizers, hydroxy acids andelectrolytes.

The compositions according to the invention can also contain otherconditioning agents. The latter may then be chosen from natural orsynthetic oils and waxes, fatty alcohols, esters of polyhydric alcohols,glycerides, silicone gums and resins or mixtures of these variouscompounds.

Of course, the person skilled in the art will be careful to choose theoptional compound or compounds to be added to the composition accordingto the invention so that the advantageous properties intrinsicallyattached to the composition in accordance with the invention are not, ornot substantially, detrimentally affected by the addition envisaged.

The compositions used according to the invention are, for example,rinsed or non-rinsed hair compositions.

They are more particularly hair-setting lotions, lotions forblow-drying, fixing compositions (lacquers) and styling compositions.The lotions can be packaged in various forms, in particular in atomizersor pump-action sprays or in aerosol containers, in order to ensureapplication of the composition in the vaporized form.

A further subject of the invention is a process for the cosmetictreatment of keratinous substances, such as hair, characterized in thatit consists in applying a cosmetic composition as defined above tokeratinous substances and in then optionally rinsing with water, afteran optional setting time.

Concrete but in no way limiting examples will now illustrate theinvention.

In the examples, AM means active material.

EXAMPLE 1

Two compositions A and B according to the invention were prepared andwere compared with compositions C and D each containing a single one ofthe two polymers. The four compositions were packaged in a pump-actionspray. A panel of 5 experienced testers evaluated the appearance of thespray and the presence or the absence of foam at the outlet of thecontainer or on the hair.

In order to evaluate the appearance of the spray, the grading rangedfrom 0 (bad), meaning that the spray was not diffuse and that thesprayed droplets were not fine, to 5 (excellent), which meant that thespray was highly diffuse and that the sprayed droplets were very fine.

In order to evaluate the presence or the absence of foam at the outletof the container or on the hair, the grading ranged from 0 (bad),meaning that there was an unacceptable copious foam, to 5 (excellent),which meant that there was no foam at all.

The results are collated/in the table below:

In g AM A B C D Ultrahold 6 4 8 — Strong⁽¹⁾ Amerhold 2 4 — 8 DR 25⁽²⁾(as copolymer) (as copolymer) (as copolymer) AMP⁽³⁾, q.s. pH 9 pH 9 pH 9pH 9 Water, q.s. for 100 100 100 100 Appearance of 4 5 1 3 the sprayAbsence or 4 5 1 4.5 presence of foam ⁽¹⁾Ultrahold Strong from BASF:acrylic acid/ethyl acrylate/N-tert-butylacrylamide terpolymer.⁽²⁾Amerhold DR 25 from Amerchol: ethyl acrylate/methylmethacrylate/methacrylic acid/acrylic acid copolymer having a glasstransition temperature of approximately 30° C. as an aqueous dispersioncomprising 25% by weight of the acrylic copolymer. ⁽³⁾AMP:2-Amino-2-methylpropanol.

The compositions A and B according to the invention had better resultsas can be seen in the table.

EXAMPLE 2

Two compositions E and F according to the invention were prepared andwere compared with compositions G and H each containing a single one ofthe two polymers. The four compositions were packaged in a pump-actionspray. A panel of 5 experienced testers evaluated the appearance of thespray and the presence or the absence of foam at the outlet of thecontainer or on the hair.

In order to evaluate the appearance of the spray, the grading rangedfrom 0 (bad), meaning that the spray was not diffuse and that thesprayed droplets were not fine, to 5 (excellent), which meant that thespray was highly diffuse and that the sprayed droplets were very fine.

In order to evaluate the presence or the absence of foam at the outletof the container or on the hair, the grading ranged from 0 (bad),meaning that there was an unacceptable copious foam, to 5 (excellent),which meant that there was no foam at all.

The results are collated in the table below:

In g AM E F G H Lovocryl 47⁽¹⁾ 6 4 8 — Amerhold 2 4 — 8 DR 25⁽²⁾ (ascopolymer) (as copolymer) (as copolymer) AMP⁽³⁾, q.s. 9 9 9 9 pH Water,q.s. for 100 100 100 100 Appearance of 5 5 2 3 the spray Absence or 5 53 4.5 presence of foam ⁽¹⁾Lovocryl 47 from National Starch:Octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer (CTFA).⁽²⁾Amerhold DR 25 from Amerchol: ethyl acrylate/methylmethacrylate/methacrylic acid/acrylic acid copolymer having a glasstransition temperature of approximately 30° C. as an aqueous dispersioncomprising 25% by weight of the acrylic copolymer. ⁽³⁾AMP:2-Amino-2-methylpropanol.

The compositions E and F according to the invention had a diffuse sprayand there was no foam at the outlet of the pump-action spray or on thehair.

EXAMPLE 3

A composition J according to the invention was prepared and was comparedwith the compositions K and L, each containing a single one of the twopolymers. The three compositions were packaged as an aerosol. A panel of5 experienced testers evaluated the appearance of the spray and theabsence or the presence of foam at the outlet of the container or on thehair.

In order to evaluate the appearance of the spray, the grading rangedfrom 0 (bad), meaning that the spray was not diffuse and that thesprayed droplets were not fine, to 5 (excellent), which meant that thespray was highly diffuse and that the sprayed droplets were very fine.

In order to evaluate the presence or the absence of foam at the outletof the container or on the hair, the grading ranged from 0 (bad),meaning that there was an unacceptable copious foam, to 5 (excellent),which meant that there was no foam at all.

The results are collated in the table below:

In g AM J K L Ultrahold 2 4 — Strong⁽¹⁾ Amerhold DR 25⁽²⁾ 2 — 4 (ascopolymer) (as copolymer) AMP⁽³⁾, q.s. pH 7 7 7 Ethanol 20 20 20 Water41 41 41 DME⁽⁴⁾ 35 35 35 Appearance of the 5 2 4 spray Absence of foam 51 4 ⁽¹⁾Ultrahold Strong from BASF: acrylic acid/ethylacrylate/N-tert-butylacrylamide terpolymer. ⁽²⁾Amerhold DR 25 fromAmerchol: ethyl acrylate/methyl methacrylate/methacrylic acid/acrylicacid copolymer having a glass transition temperature of approximately30° C. as an aqueous dispersion comprising 25% by weight of thecopolymer. ⁽³⁾AMP: 2-Amino-2-methylpropanol. ⁽⁴⁾DME: Dimethyl ethyl(propellant).

The composition J according to the invention had a diffuse spray andthere was no foam at the outlet of the aerosol or on the hair.

EXAMPLE 4

A concrete example is given here of a composition according to theinvention pressurized as an aerosol with the following composition:

Octylacrylamide/acrylates/butylaminoethyl 2 g AM methacrylate copolymer(Lovocryl 47 from National Starch) Ethyl acrylate/methyl methacrylate/ 3g AM methacrylic acid/acrylic acid terpolymer sold as an aqueousdispersion containing 25% of AM under the name Amerhold DR 25 byAmerchol 2-Amino-2-methyl-1-propanol q.s. pH 9 Ethanol 20 g Dimethylether 35 g Water q.s. for 100 g

EXAMPLE 5

A concrete example is given here of a composition according to theinvention packaged in a pump-action spray with the followingcomposition:

Dimethylaminoethyl methacrylate/ 2 g AMvinylcaprolactam/vinylpyrrolidone terpolymer as a solution in ethanolcontaining 37% of AM (Gaffix VC 713 from ISP) Ethyl acrylate/methylmethacrylate/methacrylic 2 g AM acid/acrylic acid terpolymer sold as anaqueous dispersion containing 25% of AM under the name Amerhold DR 25 byAmerchol 2-Amino-2-methyl-1-propanol q.s. pH 7 Water q.s. for 100 g

EXAMPLE 6

A concrete example is given here of a composition according to theinvention packaged in a pump-action spray with the followingcomposition:

Methacrylic acid/hydroxyester methacrylate/ 4 g AM butyl acrylate/methylmethacrylate tetrapolymer sold as an aqueous dispersion containing 41%of active material under the name Acudyne 255 by the company SeppicEthyl acrylate/methyl methacrylate/ 2 g AM methacrylic acid/acrylic acidterpolymer sold as an aqueous dispersion containing 25% of AM under thename Amerhold DR 25 by Amerchol 2-Amino-2-methyl-1-propanol q.s. pH 7Water q.s. for 100 g

1. A cosmetic composition comprising: an ethyl acrylate/methylmethacrylate/methacrylic acid/acrylic acid copolymer; and a polymerchosen from acrylates/hydroxyesters acrylates copolymers, wherein theratio by weight of the at least one acrylates/hydroxyesters acrylatescopolymers to the at least one ethyl acrylate/methylmethacrylate/methacrylic acid/acrylic acid copolymer is from 0.1:1 to10:1.
 2. A cosmetic composition according to claim 1, wherein said ethylacrylate/methyl methacrylate/methacrylic acid/acrylic acid copolymer hasa glass transition temperature of approximately 30° C. as an aqueousdispersion comprising 25% by weight of the copolymer.
 3. A cosmeticcomposition comprising: an acrylates copolymer; and a polymer chosenfrom acrylates/hydroxyesters acrylates copolymers, wherein the ratio byweight of the acrylates/hydroxyesters acrylates copolymers to theacrylates copolymer is from 0.1:1 to 10:1.
 4. A hair spray comprising:an ethyl acrylate/methyl methacrylate/methacrylic acid/acrylic acidcopolymer; and a polymer chosen from acrylates/hydroxyesters acrylatescopolymers, wherein the ratio by weight of the acrylates/hydroxyestersacrylates copolymers to the ethyl acrylate/methylmethacrylate/methacrylic acid/acrylic acid copolymer is from 0.1:1 to10:1.
 5. A hair spray according to claim 4, wherein said ethylacrylate/methyl methacrylate/methacrylic acid/acrylic acid copolymer hasa glass transition temperature of approximately 30° C. as an aqueousdispersion comprising 25% by weight of the copolymer.
 6. A hair sprayaccording to claim 5, further comprising a propellant.
 7. A hair sprayaccording to claim 6, wherein said propellant is chosen from fluorinatedhydrocarbons.
 8. A hair spray comprising: an acrylates copolymer; and apolymer chosen from acrylates/hydroxyesters acrylates copolymers,wherein the ratio by weight of the acrylates/hydroxyesters acrylatescopolymers to the acrylates copolymer is from 0.1:1 to 10:1.
 9. A hairspray according to claim 8, further comprising a propellant.
 10. Acosmetic composition comprising: an ethyl acrylate/methylmethacrylate/methacrylic acid/acrylic acid copolymer; a polymer chosenfrom acrylates/hydroxyesters acrylates copolymers; water; and analcohol; wherein the ratio by weight of the acrylates/hydroxyestersacrylates copolymers to the ethyl acrylate/methylmethacrylate/methacrylic acid/acrylic acid copolymer is from 0.1:1 to10:1.
 11. A cosmetic composition according to claim 10, furthercomprising: aminomethylpropanol; a fragrance; a preserving agent; aconditioning agent; a basifying agent other than aminomethylpropanol;and a protein.
 12. A hair spray comprising: an ethyl acrylate/methylmethacrylate/methacrylic acid/acrylic acid copolymer; a polymer chosenfrom acrylates/hydroxyesters acrylates copolymers; water; and analcohol; wherein the ratio by weight of the acrylates/hydroxyestersacrylates copolymers to the ethyl acrylate/methylmethacrylate/methacrylic acid/acrylic acid copolymer is from 0.1:1 to10:1.
 13. A hair spray according to claim 12 further comprising:aminomethylpropanol; a fragrance; a preserving agent; a conditioningagent; a basifying agent other than aminomethylpropanol; and a protein.14. A hair spray according to claim 12 wherein said ethylacrylate/methyl methacrylate/methacrylic acid/acrylic acid copolymer isat least partially neutralized.
 15. A cosmetic composition comprising:an acrylates copolymer; and a methacrylic acid/hydroxyestermethacrylate/butyl acrylate/methyl methacrylate tetrapolymer, whereinthe ratio by weight of the methacrylic acid/hydroxyestermethacrylate/butyl acrylate/methyl methacrylate tetrapolymer to theacrylates copolymer is from 0.1:1 to 10:1.
 16. A cosmetic compositionaccording to claim 15 wherein said methacrylic acid/hydroxyestermethacrylate/butyl acrylate/methyl methacrylate tetrapolymer is anaqueous dispersion containing 41% of active material.
 17. A hair spraycomprising: an ethyl acrylate/methyl methacrylate/methacrylicacid/acrylic acid copolymer; and a methacrylic acid/hydroxyestermethacrylate/butyl acrylate/methyl methacrylate tetrapolymer, whereinthe ratio by weight of the methacrylic acid/hydroxyestermethacrylate/butyl acrylate/methyl methacrylate tetrapolymer to theethyl acrylate/methyl methacrylate/methacrylic acid/acrylic acidcopolymer is from 0.1:1 to 10:1.
 18. A hair spray according to claim 17,wherein said methacrylic acid/hydroxyester methacrylate/butylacrylate/methyl methacrylate tetrapolymer is an aqueous dispersioncontaining 41% of active material.
 19. An aerosol hair spray comprising:an ethyl acrylate/methyl methacrylate/methacrylic acid/acrylic acidcopolymer; and a methacrylic acid/hydroxyester methacrylate/butylacrylate/methyl methacrylate tetrapolymer, wherein the ratio by weightof the methacrylic acid/hydroxyester methacrylate/butyl acrylate/methylmethacrylate tetrapolymer to the ethyl acrylate/methylmethacrylate/methacrylic acid/acrylic acid copolymer is from 0.1:1 to10:1.
 20. A pump action hair spray comprising: an ethyl acrylate/methylmethacrylate/methacrylic acid/acrylic acid copolymer; and a methacrylicacid/hydroxyester methacrylate/butyl acrylate/methyl methacrylatetetrapolymer, wherein the ratio by weight of the methacrylicacid/hydroxyester methacrylate/butyl acrylate/methyl methacrylatetetrapolymer to the ethyl acrylate/methyl methacrylate/methacrylicacid/acrylic acid copolymer is from 0.1:1 to 10:1.
 21. A pump actionhair spray comprising: an ethyl acrylate/methyl methacrylate/methacrylicacid/acrylic acid copolymers a polymer chosen fromacrylates/hydroxyesters acrylates copolymers; water; and an alcohol;wherein the ratio by weight of the acrylates/hydroxyesters acrylatescopolymers to the ethyl acrylate/methyl methacrylate/methacrylicacid/acrylic acid copolymer is from 0.1:1 to 10:1.
 22. A hair sprayaccording to claim 21 further comprising: aminomethylpropanol; afragrance; a preserving agent; a conditioning agent; a basifying agentother than aminomethylpropanol; and a protein.
 23. An aerosol hair spraycomprising: an ethyl acrylate/methyl methacrylate/methacrylicacid/acrylic acid copolymers a polymer chosen fromacrylates/hydroxyesters acrylates copolymers; water; propellant; and analcohol; wherein the ratio by weight of the acrylates/hydroxyestersacrylates copolymers to the ethyl acrylate/methylmethacrylate/methacrylic acid/acrylic acid copolymer is from 0.1:1 to10:1.
 24. A hair spray according to claim 23 further comprising:aminomethylpropanol; a fragrance; a preserving agent; a basifying agentother than aminomethylpropanol; and a protein.